Polymer, curable resin composition, and resin cured product

Abstract

To provide a polymer, a curable resin composition, and a resin cured product which are excellent in heat resistance and followability.SOLUTION: The polymer according to the present disclosure contains a structural unit represented by the following formula (I) and a structural unit having a glycidyl group. [In the formula (I), R1 represents a hydrogen atom or a methyl group; M represents an alkylene group or an alkylene oxide chain; and R2 represents an alkyl group or an aryl group.]SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a polymer, a curable resin composition, and a cured resin. [Background technology]

[0002] Adhesive films are used when manufacturing semiconductor devices. As a thermosetting resin composition for forming an adhesive film, a thermosetting resin composition containing an acrylic resin and a curing accelerator is known (for example, see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-190964 A Summary of the Invention [Problem to be solved by the invention]

[0004] A thermosetting resin composition used in an adhesive film is required to have excellent heat resistance and conformability. Conventional thermosetting resin compositions need to be improved in terms of achieving both heat resistance and conformability. The present disclosure aims to provide a novel polymer, a curable resin composition, and a resin cured product that are excellent in heat resistance and conformability. [Means for solving the problem]

[0005] This disclosure includes the following [1] to [5]. [1] A polymer according to one embodiment of the present disclosure includes a structural unit represented by formula (I) described below and a structural unit having a glycidyl group. [2] In the above [1], the content of the structural unit represented by formula (I) may be 5 mass % or more based on the total amount of the polymer. [3] A curable resin composition according to one embodiment of the present disclosure includes the polymer described in [1] or [2] above. [4] A cured resin product according to one embodiment of the present disclosure includes a component derived from the polymer described in [1] or [2] above. [5] A cured resin product according to one embodiment of the present disclosure includes a cured product of the curable resin composition described in [3] above. Effect of the Invention

[0006] According to the present disclosure, it is possible to provide a novel polymer, a curable resin composition, and a cured resin product that are excellent in heat resistance and conformability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Hereinafter, embodiments of the present disclosure will be described. However, the present disclosure is not limited to the following embodiments.

[0008] In this specification, the numerical range indicated by using "~" indicates a range including the numerical values ​​described before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit of a certain stage may be replaced with the upper limit or lower limit of the numerical range of another stage. In addition, in the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with a value shown in the examples. In addition, the upper limit and lower limit values ​​described individually can be arbitrarily combined. In the expression of a numerical range "A~B", the numerical values ​​A and B at both ends are included in the numerical range as the lower limit and upper limit, respectively. In this specification, for example, the description "10 or more" means "10" and "a numerical value exceeding 10", and the same applies when the numerical values ​​are different. In addition, for example, the description "10 or less" means "10" and "a numerical value less than 10", and the same applies when the numerical values ​​are different.

[0009] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate, and the same applies to other similar expressions such as (meth)acryloyl.

[0010] Unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. When a composition contains a plurality of substances corresponding to each component, the amount or content of each component means the total amount of the plurality of substances present in the composition, unless otherwise specified.

[0011] [Polymer] The polymer according to this embodiment includes a structural unit represented by the following formula (I) (hereinafter also referred to as a "first structural unit") and a structural unit having a glycidyl group (hereinafter also referred to as a "second structural unit").

[0012] The polymer according to the present embodiment has excellent heat resistance and conformability due to the inclusion of the first structural unit and the second structural unit. In particular, the polymer according to the present embodiment has excellent heat resistance due to the inclusion of the first structural unit and thus has an amide group in the side chain, and also has excellent conformability because the viscosity can be controlled by utilizing the interaction due to hydrogen bonds between the amide groups.

[0013] [ka]

[0014] In formula (I), R 1 represents a hydrogen atom or a methyl group, M represents an alkylene group or an alkylene oxide chain, R 2 represents an alkyl group or an aryl group.

[0015] The number of carbon atoms in the alkylene group may be 1 to 6, 1 to 4, or 1 to 3. The number of repeating alkylene oxides in the alkylene oxide chain may be 1 to 10, 1 to 8, or 1 to 6, and the number of carbon atoms in the alkylene oxide may be 2 to 10, 2 to 6, or 2 to 4. M may be a methylene group, an ethylene group, a propylene group, a butylene group, an ethylene oxide chain, or a propylene oxide chain.

[0016] The number of carbon atoms in the alkyl group may be 1 to 20, 2 to 10, or 3 to 6. The number of carbon atoms in the aryl group may be 6 to 20, 6 to 15, or 6 to 10. R 2 may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, or a phenyl group.

[0017] An example of a monomer that provides the first structural unit is a monomer represented by the following formula (II) (hereinafter, also referred to as an "amide monomer"). The amide monomer has a (meth)acryloyloxy group and an amide group. 1 , M and R 2 are R in formula (I), 1 , M and R 2 is the same as: CH2=CR 1 -COO-M-NH-COR 2 (II)

[0018] The amide monomer may be appropriately produced or may be a commercially available product. The amide monomer may be produced, for example, by a method including a step 1 of reacting an aryl carboxylic acid chloride or an alkyl carboxylic acid chloride with a hydroxyalkylamine or a polyoxyalkyleneamine, and a step 2 of reacting the reaction product obtained in the step 1 with (meth)acryloyl chloride to obtain an amide monomer. An example of the aryl carboxylic acid chloride is benzoyl chloride, and an example of the alkyl carboxylic acid compound is butyryl chloride. An example of the hydroxyalkylamine is 2-aminoethanol.

[0019] The content of the first structural unit in the polymer may be 5% by mass or more, 6% by mass or more, 8% by mass or more, or 10% by mass or more based on the total amount of the polymer from the viewpoints of heat resistance and conformability, and may be 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less from the viewpoints of handleability and adhesiveness. The content of the first structural unit in the polymer may be 5% by mass to 50% by mass, 6% by mass to 45% by mass, 8% by mass to 40% by mass, or 10% by mass to 35% by mass based on the total amount of the polymer.

[0020] The monomer that provides the second structural unit may, for example, include a compound having an ethylenically unsaturated group and an epoxy group.Such a compound may, for example, include glycidyl (meth)acrylate, α-ethyl glycidyl (meth)acrylate, α-propyl glycidyl (meth)acrylate, α-butyl glycidyl (meth)acrylate, 2-methyl glycidyl (meth)acrylate, 2-ethyl glycidyl (meth)acrylate, 2-propyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxyheptyl (meth)acrylate, α-ethyl-6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

[0021] The content of the second structural unit in the polymer may be 0.5% by mass or more, 1.0% by mass or more, or 1.5% by mass or more based on the total amount of the polymer from the viewpoint of the handleability of the polymer, and may be 20% by mass or less, 15% by mass or less, or 10% by mass or less from the viewpoint of the followability. The content of the second structural unit in the polymer may be 0.5% by mass to 20% by mass, 1.0% by mass to 15% by mass, or 1.5% by mass to 10% by mass based on the total amount of the polymer.

[0022] The polymer may further include other structural units than the first structural unit and the second structural unit, as long as the effect of the present disclosure is not impaired. Examples of monomers that provide other structural units include (meth)acrylic acid, styrene, alkyl (meth)acrylate, (meth)acrylonitrile, and benzyl (meth)acrylate. The polymer may be a (meth)acrylic copolymer.

[0023] The number of carbon atoms of the alkyl group in the alkyl (meth)acrylate may be 1 to 20, 1 to 10, or 2 to 6. Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, and dodecyl (meth)acrylate. The content of the structural unit based on the alkyl (meth)acrylate may be 30% by mass or more, 40% by mass or more, or 50% by mass or more based on the total amount of the polymer.

[0024] The content of structural units based on (meth)acrylonitrile may be 15 mass % or more, 20 mass % or more, or 25 mass % or more, based on the total amount of the polymer.

[0025] The weight average molecular weight (Mw) of the polymer may be 10,000 or more, 50,000 or more, or 70,000 or more from the viewpoint of heat resistance and film-forming property, and may be 1,000,000 or less, 500,000 or less, 250,000 or less, 200,000 or less, 150,000 or less, or 100,000 or less from the viewpoint of tracking property. Mw can be measured by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. Mw can be measured, for example, by the method described in the Examples.

[0026] The polymer can be obtained, for example, by polymerizing monomers by radical polymerization using a solution polymerization method. More specifically, the polymer can be obtained by polymerizing monomers including a monomer that provides a first structural unit and a monomer that provides a second structural unit in a solvent.

[0027] The solvent can be appropriately selected from organic solvents commonly used in the field of radical polymerization. Examples of the solvent include toluene and 1-methoxy-2-propanol. The solvent may be used alone or in combination of two or more. The amount of the solvent used can be appropriately set depending on the type of monomer, reaction conditions, solid content concentration, etc.

[0028] When polymerizing the monomer, a thermal radical generator may be added as necessary. Examples of the thermal radical generator include azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl-2,2'-azobis(2-methylpropionate). The amount of the thermal radical generator added may be appropriately set depending on the type of monomer, reaction conditions, etc., and is not particularly limited, but may be 0.01% by mass or more or 0.05% by mass or more, and 1.0% by mass or less or 0.5% by mass or less, based on the total amount of the monomer.

[0029] The polymerization temperature may be from 60° C. to 100° C., or from 70° C. to 100° C. The polymerization time may be from 1 hour to 15 hours, or from 5 hours to 10 hours.

[0030] [Curable resin composition] The curable resin composition according to the present embodiment includes the above-mentioned polymer. The curable resin composition is thermosetting and can be in a semi-cured (B stage) state and then in a completely cured (C stage) state after a curing process. The curable resin composition may further contain various other components depending on the application. Examples of the other components include an epoxy resin (excluding the above-mentioned polymer), a curing agent, a curing accelerator, an inorganic filler, and a coupling agent.

[0031] Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, stilbene type epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, triphenolmethane type epoxy resins, biphenyl type epoxy resins, xylylene type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, polyfunctional phenols, and diglycidyl ether compounds of polycyclic aromatics such as anthracene.

[0032] The curing agent is not particularly limited as long as it is a component that can be a curing agent for epoxy resin. Examples of the curing agent include phenolic resins and active ester resins. Examples of the phenolic resin include novolac-type phenolic resins obtained by condensing or co-condensing phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, and a compound having an aldehyde group such as formaldehyde under an acid catalyst, allylated bisphenol A, allylated bisphenol F, allylated naphthalenediol, phenol novolac, phenol aralkyl resins synthesized from phenols such as phenol and / or naphthols and dimethoxyparaxylene or bis(methoxymethyl)biphenyl, naphthol aralkyl resins, biphenyl aralkyl-type phenolic resins, and phenyl aralkyl-type phenolic resins. Examples of active ester resins include ester compounds composed of an aliphatic or aromatic carboxylic acid compound, an aliphatic hydroxy compound, an aromatic hydroxy compound (phenol compound), an aromatic thiol compound (thiophenol compound), an N-hydroxyamine compound, or a heterocyclic hydroxy compound.

[0033] Examples of the hardening accelerator include imidazole compounds, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. Examples of the imidazole compounds include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole.

[0034] Examples of inorganic fillers include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, boron nitride, crystalline silica, and amorphous silica. The inorganic filler may be surface-treated with a surface treatment agent from the viewpoint of compatibility of the surface with a solvent, other components, and the like, and adhesive strength. Examples of surface treatment agents include silane-based coupling agents. Examples of functional groups of silane-based coupling agents include vinyl groups, (meth)acryloyl groups, epoxy groups, mercapto groups, amino groups, diamino groups, alkoxy groups, and ethoxy groups.

[0035] Examples of the coupling agent include a silane-based coupling agent, a titanate-based coupling agent, and an aluminum-based coupling agent.Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, and the like. , γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyltrimethoxysilane, γ-(N-methyl)anilinopropyltrimethoxysilane, γ-(N-ethyl)anilinopropyltrimethoxysilane, γ-(N,N-di γ-(N,N-dimethyl)aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-dibutyl)aminopropyltriethoxysilane, γ-(N-methyl)anilinopropyltriethoxysilane, γ-(N-ethyl)anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N,N-dibutyl)aminopropylmethyldimethoxysilane, γ-(N-methyl)aminopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N,N-dibutyl)aminopropylmethyldimethoxysilane, Examples of suitable silanes include anilinopropyl methyldimethoxysilane, γ-(N-ethyl)anilinopropyl methyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-ureidopropyltriethoxysilane.

[0036] The curable resin composition may be used as a varnish of the curable resin composition diluted with a solvent. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more. Among these, the solvent may be toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone from the viewpoints of solubility and boiling point.

[0037] The varnish of the curable resin composition can be prepared by mixing and kneading the above-mentioned polymer, other components and solvent. The order of mixing and kneading each component is not particularly limited and can be set appropriately. Mixing and kneading can be performed by appropriately combining a dispersing machine such as a normal stirrer, a mortar and pestle, a three-roll mill, a ball mill, or a bead mill.

[0038] The curable resin composition according to this embodiment contains the above-mentioned polymer, and therefore has excellent heat resistance and conformability, and can be used as a thermosetting resin composition for use in an adhesive film for a semiconductor device.

[0039] [Cured resin] The cured resin according to the present embodiment includes a component derived from the above-mentioned polymer or curable resin composition. The cured resin may be a cured product of the above-mentioned polymer or a cured product of the above-mentioned curable resin composition. The cured resin can be formed, for example, by applying a solution of the polymer or a varnish of the curable resin composition to a support film and drying it by heating.

[0040] Examples of the support film include films of polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polyimide, and the like.

[0041] The coating method may be a known method, such as knife coating, roll coating, spray coating, gravure coating, bar coating, and curtain coating. The conditions for heat drying are not particularly limited as long as the solvent used is sufficiently volatilized, and may be, for example, 50 to 200° C. for 1 to 90 minutes.

[0042] The cured resin may be in the form of a film. The thickness of the cured resin may be appropriately adjusted depending on the application. From the viewpoint of sufficiently filling the unevenness of the semiconductor element (semiconductor chip), wire, wiring circuit of the substrate, etc., the thickness of the cured resin may be 5 to 200 μm, 10 to 110 μm, or 15 to 80 μm. EXAMPLES

[0043] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0044] [Synthesis of Monomer] (Synthesis Example 1) Benzoyl chloride (4.8 mL; 0.041 mol) was slowly added dropwise to a dichloromethane (100 mL) solution of 2-aminoethanol (12 mL; 0.20 mol) cooled in an ice bath while stirring. After the dropwise addition, the mixture was stirred at the same temperature for 15 minutes. Next, the ice bath was removed, and the mixture was stirred at room temperature (25°C, the same applies below) for another 16 hours. Dichloromethane was then distilled off under reduced pressure to obtain crude product 1. Crude product 1 was purified by silica gel column chromatography (silica gel: PSQ60B manufactured by Fuji Silysia Chemical Co., Ltd., dichloromethane:methanol = 20:1 (V / V) (developing solvent, about 200 mL)) to obtain N-(2-hydroxyethyl)benzamide (6.9 g; 0.041 mol) as a colorless solid. The reaction scheme of N-(2-hydroxyethyl)benzamide is as follows.

[0045] [ka]

[0046] Triethylamine (7.6 mL; 0.055 mol) was added to a dichloromethane (100 mL) solution of N-(2-hydroxyethyl)benzamide (6.9 g; 0.041 mol) cooled in an ice bath while stirring. Next, acryloyl chloride (4.1 mL; 0.050 mol) was slowly added dropwise. After the dropwise addition, the mixture was stirred at the same temperature for 5 minutes. Next, the ice bath was removed, and the mixture was stirred at room temperature for another 24 hours to react. Then, dichloromethane was distilled off under reduced pressure to obtain crude product 2. Crude product 2 was purified by silica gel column chromatography (silica gel: Fuji Silysia Chemical Co., Ltd. PSQ60B, hexane:ethyl acetate = 2:1 → 1:1 → 2:3 (V / V) (developing solvent, about 600 mL)) to obtain amide monomer A1 (7.4 g; 0.034 mol; yield: 83%) as a milky white solid. The reaction scheme of amide monomer A1 is as follows.

[0047] [ka]

[0048] (Synthesis Example 2) Amide monomer A2 was obtained in the same manner as in Synthesis Example 1, except that butyryl chloride was used instead of benzoyl chloride in Synthesis Example 1.

[0049] [ka]

[0050] (Synthesis Example 3) 2-isocyanatoethyl methacrylate (10.1 g; 0.065 mol) was slowly added dropwise to a solution of butylamine (4.8 g; 0.065 mol) in dehydrated toluene (80 g) cooled in an ice bath while stirring. Thirty minutes after the end of the dropwise addition, the mixture was slowly returned to room temperature and stirred at room temperature for 6 hours to react. Toluene was then distilled off under reduced pressure, and the mixture was dried under reduced pressure at 40°C for 2 hours. The obtained crude product was dissolved in the minimum amount of acetone that could dissolve it, and the solution was slowly added dropwise to hexane while stirring. The precipitate was separated into solid and liquid, and then dried under reduced pressure at 40°C for 4 hours to obtain Monomer A3 containing a urea group.

[0051] [ka]

[0052] [Polymer] Example 1 Solution (a) was prepared by adding 15.1 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 3:2 (mass ratio)) to 11.1 g of acrylonitrile, 5.4 g of ethyl acrylate, 14.6 g of butyl acrylate, 1.3 g of glycidyl methacrylate, and 5.4 g of amide monomer A1. Separately, solution (b) was prepared by adding 0.038 g of azobisisobutyronitrile to 10.0 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 3:2 (mass ratio)). After both solutions were deoxygenated by passing nitrogen through, solution (a) was heated to 75 ° C., and solution (b) was slowly dropped into solution (a) while stirring and mixed. Two hours after the dropwise addition, the temperature was increased from 75°C to 85°C, and two hours later, the temperature was increased from 85°C to 95°C, and then maintained for four hours. The mixture was then cooled to room temperature to obtain a solution of polymer B1 (solid content: 55% by mass). The Mw of polymer B1 was 76,800.

[0053] Example 2 Except for using the amide monomer A2 instead of the amide monomer A1, the same operation as in Example 1 was carried out to obtain a solution of polymer B2 (solid content: 55% by mass). The Mw of polymer B2 was 70,500.

[0054] Comparative Example 1 A commercially available acrylic polymer B3 (product name: HTR-860P-3; manufactured by Nagase ChemteX Corporation; Mw: 860,000; not containing a first constitutional unit) was prepared.

[0055] Comparative Example 2 Except for using Monomer A3 instead of Amide Monomer A1, the same procedure as in Example 1 was carried out to obtain a solution of Polymer B4 (solid content: 55% by mass). The Mw of Polymer B4 was 64,300.

[0056] (Measurement of Mw) The Mw was measured by gel permeation chromatography (GPC) and calculated using a calibration curve of standard polystyrene. The GPC conditions are shown below. Measuring device: Showdex (registered trademark) GPC-101 (Resonac Co., Ltd.) Detector: Differential refractometer Shodex RI-71S (Resonac Co., Ltd.) Column: Shodex LF-804+LF-804 (Resonac Co., Ltd.) Column temperature: 40℃ Eluent: tetrahydrofuran (THF) Flow rate: 1mL / min

[0057] [evaluation] (Easy to handle and follow-up) The polymer solutions (solid content: 1 g) prepared in the Examples and Comparative Examples and a curing accelerator (solid content: 0.01 g; product name: 2PZ-CN; manufactured by Shikoku Chemical Industry Co., Ltd.; 1-cyanoethyl-2-phenylimidazole) were added to a plastic container, and then an organic solvent (cyclohexanone) was added so that the NV value ([mass of paint after drying] / [mass of paint before drying]×100) was 30 mass%, and the mixture was thoroughly stirred and degassed using a planetary stirrer to prepare a coating liquid.

[0058] A coating solution was applied onto a polyethylene terephthalate (PET) film using a precision coating device, and then the film was heated in a dryer at 100°C for 10 minutes to produce a resin film 1 with a thickness of 15 μm. 12 layers of the resin film 1 were stacked and laminated at 80°C and 0.4 MPa for 20 seconds to produce an evaluation sample (thickness: about 180 μm). A sample stage with a diameter of 8 mm was placed on a viscoelasticity measuring device (product name: ARES G2; manufactured by TA Instruments), and the evaluation sample was set on the sample stage. The complex viscosity was measured while increasing the temperature from 30°C to 160°C at a heating rate of 5°C / min.

[0059] The ease of handling and the followability of each sample were evaluated based on the complex viscosity at 30°C and 150°C. Specifically, the ease of handling was evaluated when the complex viscosity at 30°C was 3.0×10 4Pa s or more, A is 3.0×10 4 A complex viscosity of 150°C or less was rated as B, and a complex viscosity of less than 5000 Pa·s at 150°C was rated as A, and a complex viscosity of 5000 Pa·s or more was rated as B. The evaluation results are shown in Table 1. The complex viscosity at 30°C indicates the viscosity at around room temperature, so a high complex viscosity at 30°C can suppress tack and exudation, improving handleability. The complex viscosity at 150°C can indicate the viscosity of the resin when a resin layer is used for embedding and molding in a circuit board or the like, so a low complex viscosity at 150°C can allow the resin to follow the recesses of the circuit board, improving followability.

[0060] (Heat resistance) The polymer solutions prepared in the examples and comparative examples were applied onto a PET film and dried at 140°C for 2 hours to form a resin film 2. The resin film 2 was heated from room temperature to 400°C at 10°C / min in an air flow of 100mL / min using a thermogravimetric analyzer (TGA) (apparatus name: DTG-60H; manufactured by Shimadzu Corporation), and the mass at 100°C (hereinafter also referred to as "W1") and the mass at 280°C (hereinafter also referred to as "W2") were measured. The mass at 100°C was used as the standard, and the mass reduction rate at 280°C (hereinafter also referred to as "mass reduction rate") was calculated by the following formula (1). The heat resistance was evaluated by rating A when the mass reduction rate was less than 5.0% and B when the mass reduction rate was 5.0% or more. The evaluation results are shown in Table 1. Mass reduction rate (%)=(W1-W2) / W1×100 (1)

[0061] [Table 1]

Claims

1. A polymer comprising a structural unit represented by the following formula (I) and a structural unit having a glycidyl group: 【Chemistry 1】 [In formula (I), R １ represents a hydrogen atom or a methyl group, M represents an alkylene group or an alkylene oxide chain, R ２ represents an alkyl group or an aryl group.

2. The polymer according to claim 1 , wherein the content of the structural unit represented by formula (I) is 5 mass % or more based on the total amount of the polymer.

3. A curable resin composition comprising the polymer according to claim 1 or 2.

4. A cured resin comprising a component derived from the polymer according to claim 1 or 2.

5. A cured resin product comprising the cured product of the curable resin composition according to claim 3.

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